WO2006015743A1 - Verfahren zur herstellung hochmolekularer polyamide - Google Patents
Verfahren zur herstellung hochmolekularer polyamide Download PDFInfo
- Publication number
- WO2006015743A1 WO2006015743A1 PCT/EP2005/008275 EP2005008275W WO2006015743A1 WO 2006015743 A1 WO2006015743 A1 WO 2006015743A1 EP 2005008275 W EP2005008275 W EP 2005008275W WO 2006015743 A1 WO2006015743 A1 WO 2006015743A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyamide
- molecular weight
- compound
- polyamides
- high molecular
- Prior art date
Links
- 239000004952 Polyamide Substances 0.000 title claims abstract description 137
- 229920002647 polyamide Polymers 0.000 title claims abstract description 137
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 23
- 239000005749 Copper compound Substances 0.000 claims description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 21
- 239000004202 carbamide Substances 0.000 claims description 21
- 150000001880 copper compounds Chemical class 0.000 claims description 21
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 13
- -1 poly (nonamethylene) urea Polymers 0.000 claims description 12
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 11
- 239000010408 film Substances 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 239000006260 foam Substances 0.000 claims description 7
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 5
- WNVQBUHCOYRLPA-UHFFFAOYSA-N triuret Chemical compound NC(=O)NC(=O)NC(N)=O WNVQBUHCOYRLPA-UHFFFAOYSA-N 0.000 claims description 5
- DRNXZGJGRSUXHW-UHFFFAOYSA-N silyl carbamate Chemical compound NC(=O)O[SiH3] DRNXZGJGRSUXHW-UHFFFAOYSA-N 0.000 claims description 3
- UXLVQUDJEAWBPQ-UHFFFAOYSA-N trimethylsilyl carbamate Chemical compound C[Si](C)(C)OC(N)=O UXLVQUDJEAWBPQ-UHFFFAOYSA-N 0.000 claims description 3
- AATYKEFFPLPLST-UHFFFAOYSA-N trimethylsilylurea Chemical compound C[Si](C)(C)NC(N)=O AATYKEFFPLPLST-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 28
- 229920002292 Nylon 6 Polymers 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 235000013877 carbamide Nutrition 0.000 description 21
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 14
- 239000008187 granular material Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000000654 additive Substances 0.000 description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 12
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 229920002302 Nylon 6,6 Polymers 0.000 description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 7
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 7
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 5
- 229920000299 Nylon 12 Polymers 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 description 4
- 229920000305 Nylon 6,10 Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 229960004217 benzyl alcohol Drugs 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003672 ureas Chemical class 0.000 description 3
- HCUZVMHXDRSBKX-UHFFFAOYSA-N 2-decylpropanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)C(O)=O HCUZVMHXDRSBKX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229920003189 Nylon 4,6 Polymers 0.000 description 2
- 229920000572 Nylon 6/12 Polymers 0.000 description 2
- 229920000577 Nylon 6/66 Polymers 0.000 description 2
- 229920000393 Nylon 6/6T Polymers 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920002614 Polyether block amide Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- OBRMNDMBJQTZHV-UHFFFAOYSA-N cresol red Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(C)C(O)=CC=2)=C1 OBRMNDMBJQTZHV-UHFFFAOYSA-N 0.000 description 2
- GMAYNBHUHYFCPZ-UHFFFAOYSA-N cyclohexyl-(4,4-dimethylcyclohexyl)methanediamine Chemical compound C1CC(C)(C)CCC1C(N)(N)C1CCCCC1 GMAYNBHUHYFCPZ-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
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- 239000006082 mold release agent Substances 0.000 description 2
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- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
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- 229920006024 semi-aromatic copolyamide Polymers 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
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- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical class CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 description 1
- FHKPTEOFUHYQFY-UHFFFAOYSA-N 2-aminohexanenitrile Chemical compound CCCCC(N)C#N FHKPTEOFUHYQFY-UHFFFAOYSA-N 0.000 description 1
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- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- HMJBXEZHJUYJQY-UHFFFAOYSA-N 4-(aminomethyl)octane-1,8-diamine Chemical compound NCCCCC(CN)CCCN HMJBXEZHJUYJQY-UHFFFAOYSA-N 0.000 description 1
- MKNQNPYGAQGARI-UHFFFAOYSA-N 4-(bromomethyl)phenol Chemical compound OC1=CC=C(CBr)C=C1 MKNQNPYGAQGARI-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
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- 229920000049 Carbon (fiber) Polymers 0.000 description 1
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- SNPIMBDCLUUDST-UHFFFAOYSA-N aziridin-2-one Chemical compound O=C1CN1 SNPIMBDCLUUDST-UHFFFAOYSA-N 0.000 description 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- PEVZEFCZINKUCG-UHFFFAOYSA-L copper;octadecanoate Chemical compound [Cu+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O PEVZEFCZINKUCG-UHFFFAOYSA-L 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
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- 229920003244 diene elastomer Polymers 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 230000010006 flight Effects 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- QMXSDTGNCZVWTB-UHFFFAOYSA-N n',n'-bis(3-aminopropyl)propane-1,3-diamine Chemical compound NCCCN(CCCN)CCCN QMXSDTGNCZVWTB-UHFFFAOYSA-N 0.000 description 1
- PJOLOHMGBICKJH-UHFFFAOYSA-N n'-(3-aminopropyl)-n'-[2-[bis(3-aminopropyl)amino]ethyl]propane-1,3-diamine Chemical compound NCCCN(CCCN)CCN(CCCN)CCCN PJOLOHMGBICKJH-UHFFFAOYSA-N 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- JGCBNZLRTUKUAQ-UHFFFAOYSA-M sodium 4-[[4-(benzylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(S(=O)(=O)[O-])=CC=C1N=NC(C=C1)=CC=C1NCC1=CC=CC=C1 JGCBNZLRTUKUAQ-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- BPSKTAWBYDTMAN-UHFFFAOYSA-N tridecane-1,13-diamine Chemical compound NCCCCCCCCCCCCCN BPSKTAWBYDTMAN-UHFFFAOYSA-N 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/46—Post-polymerisation treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
Definitions
- the invention relates to a process for preparing high molecular weight polyamides, da ⁇ characterized in that reacting a polyamide A) at a temperature of 150 to 350 0 C with a compound B), which liberates isocyanic acid at this reaction temperature, wherein in the polyamide used A) the concentration of the amino end groups is greater than or equal to the concentration of the carboxyl end groups.
- the invention relates to the obtainable by the process high molecular weight polyamides, their use for the production of moldings, films, fibers and foams, and the moldings, films, fibers and foams from the navalmoleku ⁇ laren polyamides.
- a process has been found for increasing the molecular weight of polyamides, characterized in that a polyamide A), wherein the concentration of the amino end groups is greater than or equal to the concentration of the carboxyl end groups, at a temperature of 150 to 350 ° C with a Verbin ⁇ tion B), which releases isocyanic acid at this reaction temperature.
- High molecular weight polyamides have high melt viscosities and are particularly useful for extruding semi-finished products, e.g. Profiles, plates or rods, and used for film blowing. In these processing methods, the high melt viscosity has a favorable effect on the processability and the quality of the products obtained.
- high molecular weight polyamides are prepared in two stages: first, for example, a low molecular weight polymer is prepared in a melt condensation from the monomers, which is then subjected to a solid phase condensation is converted to the high molecular weight end product.
- the molecular weight increase should be able to be achieved by simple addition of an additive to the low molecular weight polyamide, which rapidly brings about the desired molecular weight increase.
- WO 02/26865 describes a process for reducing the content of ⁇ -caprolactam in polyamide 6 (PA 6), in which an additive, for example urea, which forms isocyanic acid by heat, either a) for the polymerization of PA 6 or b ) of a PA 6 melt is added.
- an additive for example urea, which forms isocyanic acid by heat, either a) for the polymerization of PA 6 or b ) of a PA 6 melt is added.
- the urea is added towards the end of the polymerization; in Example 15, a commercially available PA 6 granules is sprayed with a urea solution, dried and extruded at 240 to 260 0 C.
- the relative solution viscosity of the urea-treated polyamides does not differ significantly from that of the non-urea-containing comparative example. There are no indications in the text of an increase in the molecular weight. Information on the amino end group or carboxyl end group concentration in the
- the desired molecular weight increase should be achieved by simple addition of an additive to a conventional, non-high molecular weight polyamide.
- a polyamide A) is reacted at 150 to 35O 0 C with a compound B), which releases isocyanic acid at this reaction temperature.
- the concentration of the amino end groups is greater than or equal to the concentration of the carboxyl end groups (CEK, carboxyl end group concentration), ie AEK> CEK.
- the amino end group concentration is preferably greater than the carboxyl end group concentration, ie AEK> CEK.
- concentrations are, as usual, defined as the number of end groups (in moles or equivalents) per mass unit of polyamide, for example x mmol end groups per kg of polyamide.
- the determination of the amino end groups can be carried out for example by means of titration of a solution of the polyamide in the presence of an indicator.
- the polyamide A) is dissolved in a mixture of phenol and methanol (for example 75% by weight of phenol and 25% by weight of methanol) with heating.
- the mixture may be refluxed at the boiling point until the polymer is dissolved.
- the cooled solution is admixed with a suitable indicator or indicator mixture (eg methanolic solution of benzyl orange and methylene blue) and treated with a methanolic solution. containing perchloric acid solution in glycol, until the color change titrated. From the perchloric acid consumption, the amino end group concentration is calculated.
- the titration without indicator can also be carried out potentiometrically with a perchloric acid solution in ethylene glycol, as described in WO 02/26865 on page 11.
- the determination of the carboxyl end groups can be carried out e.g. likewise by titration of a solution of the polyamide using an indicator.
- the polyamide A) in benzyl alcohol (phenylmethanol) with heating, e.g. until Sie ⁇ , solved, putting on a riser and nitrogen gas introduces. Thereafter, the solution which is still hot is mixed with a suitable indicator (for example propanolic solution of cresol red) and immediately titrated with an alcoholic potassium hydroxide solution (KOH dissolved in a mixture of methanol, 1-propanol and 1-hexanol) until it turns over. From the KOH consumption, the carboxyl group concentration is calculated.
- a suitable indicator for example propanolic solution of cresol red
- the titration without indicator can also conduct conductometrically with a NaOH solution in benzyl alcohol, as described in WO 02/26865 on page 11-12.
- polyamide A all known polyamides are suitable as polyamide A), provided that they fulfill the mentioned condition AEK> CEK.
- polyamides having aliphatic, semicrystalline or partially aromatic and amorphous structures of any kind and their blends, including polyetheramides such as polyether block amides, are suitable.
- Semicrystalline or amorphous resins having a weight average molecular weight of at least 5,000 are preferred.
- examples of these are polyamides derived from lacquers with 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam, as well as polyamides obtained by reacting dicarboxylic acids with diamines.
- Suitable dicarboxylic acids are alkanedicarboxylic acids having 6 to 12, in particular 6 to 10, carbon atoms and aromatic dicarboxylic acids.
- Suitable diamines are particularly alkanediamines having 6 to 12, in particular 6 to 8 carbon atoms and m-xylylenediamine, di (4-aminophenyl) methane, di (4-amino-cyclohexyl) methane, di (4-amono-3 -methyl-cyclohexyl) -methane, isophoronediamine, 1, 5-diamino-2-methyl-pentane, 2,2-di- (4-aminophenyl) -propane or 2,2-di- (4-amino-cyclohexyl) -propane.
- Preferred polyamides are polyhexamethylene adipamide (PA 66) and polyhexamethylene sebacamide (PA 610), polycaprolactam (PA 6) and copolyamides 6/66, in particular with a content of 5 to 95% by weight of caprolactam units.
- PA 6, PA 66 and Copolyamide 6/66 are particularly preferred; PA 6 is very particularly preferred.
- polystyrene resin e.g. polystyrene resin
- PA 6 Amino capronitrile
- PA 66 adiponitrile with hexamethylenediamine
- Direct polymerization in the presence of water as described for example in DE-A 10313681, EP-A 1198491 and EP-A 922065.
- polyamide 46 1, 4-diaminobutane with adipic acid are available at elevated temperature (polyamide 46).
- Manufacturing processes for polyamides of this structure are known e.g. in EP-A 38 094, EP-A 38 582 and EP-A 39 524 described.
- polyamides which are obtainable by copolymerization of two or more of the abovementioned monomers, or mixtures of a plurality of polyamides, the mixing ratio being arbitrary.
- the triamine content is less than 0.5, preferably less than 0.3 wt .-% (see EP-A 299 444).
- the preparation of the partially aromatic copolyamides having a low triamine content can be carried out by the processes described in EP-A 129 195 and 129 196.
- PA 11 11-aminoundecanoic acid
- PA 12 laurolactam AA / BB-polymers PA 12 laurolactam AA / BB-polymers:
- PA 46 tetramethylenediamine, adipic acid
- PA 66 hexamethylene diamine, adipic acid
- PA 610 hexamethylene diamine, sebacic acid
- PA 612 hexamethylenediamine, decanedicarboxylic acid
- PA 613 hexamethylenediamine, undecanedicarboxylic acid
- PA 1212 1, 12-dodecanediamine, decanedicarboxylic acid
- PA 1313 1, 13-diaminotridecane, undecanedicarboxylic acid
- PA 6T hexamethylenediamine, terephthalic acid
- PA MXD6 m-xylylenediamine, adipic acid
- PA 6-3-T trimethylhexamethylenediamine, terephthalic acid
- PA 6 / 6T (see PA 6 and PA 6T)
- PA 6/66 (see PA 6 and PA 66)
- PA 6/12 see PA 6 and PA 12
- PA 66/6/610 see PA 66, PA 6 and PA 610
- PA 6I / 6T see PA 6I and PA 6T
- PA PA PACM 12 diaminodicyclohexylmethane, laurolactam
- PA 6I / 6T / PACM such as PA 6I / 6T + diaminodicyclohexylmethane
- PA 12 / MACMI laurolactam dimethyldiaminodicyclohexylmethane, isophthalic acid
- PA 12 / MACMT laurolactam dimethyldiaminodicyclohexylmethane, terephthalic acid
- polyamides A) and their preparation are known, for example, from Ulimann's Encyclopedia of Industrial Chemistry, 4th Edition, Vol. 19, pp. 39-54, Verlag Chemie, Weinheim 1980; Ullmann's Encyclopedia of Industrial Chemistry, Vol. A21, pp. 179-206, VCH Verlag, Weinheim 1992; Stoeckhert, Kunststofflexikon, 8th edition, pp. 425-428, Carl Hanser Verlag Kunststoff 1992 (keyword “polyamides” and following), and Saechtling, plastic paperback, 27th edition, Carl Hanser Verlag Kunststoff, 1998, pages 465-478.
- the polymerization or polycondensation of the starting monomers to the polyamide A) is preferably carried out by the usual methods.
- the polymerization of caprolactam can be carried out according to the methods described in DE-A 14 95 198 and US Pat DE-A 25 58480 described continuous process.
- the polymerization of AH salt for the preparation of PA 66 can be carried out by the usual batchwise process (see: Polymerization Processes p. 424-467, in particular p. 444-446, Interscience, New York, 1977) or by a continuous process, for example according to EP-A 129 196, carried out.
- Suitable chain regulators are e.g. Triacetonediamine compounds (see WO-A 95/28443), and bases, especially amines. Bases are preferred as chain regulators because they allow the required amino terminal excess or equilibrium (AEK> CEK) to be set in a simple manner. Suitable bases are e.g.
- Hexamethylenediamine bis (hexamethylene) triamine, benzylamine, 1,4-cyclohexyldiamine, bis (tetramethylene) triamine, 4-aminomethyl-1,8-octanediamine, tris (3-aminopropyl) amine, N, N, N ', N '-Tetra (3-amino-propyl) ethylenediamine, and the diamines mentioned above.
- chain regulators are used, their amount is generally 0.01 to 5, in particular 0.1 to 1, 5 wt .-%, based on the monomers used in the preparation of the polyamide A).
- the resulting polymer melt is discharged from the reactor, cooled and gra ⁇ nulated.
- the granules obtained can be subjected to a postpolymerization. This is done in a conventional manner by heating the granules to a temperature T below the melting temperature T 3 or crystallite melting temperature T k of the polyamide.
- the final molecular weight of the polyamide (measurable as the viscosity number VZ, see information on the VZ below) is established.
- the post-polymerization takes 2 to 24 hours, if necessary, in particular 12 to 24 hours.
- the desired molecular weight of the polyamide A) is reached, the granules are cooled in a conventional manner.
- the polyamide A) can be used instead of granules as chips, chips or other übli ⁇ cher form. Possibly. the polyamide A) is dried to a water content of 0.01 to 0.1 wt .-%, based on the polyamide A). For this one can use conventional drying devices, e.g. dry in vacuo and / or at elevated temperature.
- the method of preparation of the polyamides A) is generally not critical. It is only necessary to ensure that in the polyamide A) used, the amino end group concentration is greater than or equal to the carboxyl end group concentration.
- Suitable polyamides A) generally have a viscosity number VZ of 50 to 200, preferably 70 to 160 and particularly preferably 90 to 130 ml / g determined according to ISO 307 EN on a 0.5 wt .-% solution of the polyamide in 96 wt .-% sulfuric acid at 25 ° C.
- the molecular weight of the polyamide A) can be increased particularly easily and rapidly if at least some of the polymer chains of the polyamide A) have two or more amino end groups.
- the process is characterized in that in the polyamide A) at least 20 mol% of the polymer chains have two or more amino end groups. This proportion is particularly preferably at least 30 mol%.
- an isocyanic acid source are, for example, urea, condensation products of urea such as biuret, triuret or cyanuric acid, as well as other urea derivatives or oligomeric or polymeric urea compounds which release isocyanic acid at said reaction temperature.
- Such compounds are in particular carbamates such as silyl carbamate, trimethylsilyl carbamate, and trimethylsilylurea or poly (nonamethylene) urea.
- the compound B) is preferably selected from urea, biuret, triuret, cyanuric acid, silyl carbamate, trimethylsilyl carbamate, trimethylsilylurea and poly (nonamethylene) urea. Particular preference is given to using urea, biuret, triuret or cyanuric acid, in particular urea.
- the compound B) can be reacted as such with the polyamide A), the isocyanic acid being formed during the reaction on account of the stated temperature.
- the isocyanic acid can first be prepared separately from the stated isocyanic acid sources (for example ureas, biuret, triuret, cyanuric acid, carbamates) by thermal decomposition and then this separately prepared isocyanic acid can be reacted with the polyamide A).
- the thermal decomposition of Isocyanankladense can be triggered by heating, or by energy input via elekt ⁇ romagnetician radiation.
- the amount of the compound B) is 0.001 to 10 wt .-%, preferably
- compound B) in an amount such that the molar ratio of compound B) to the amino end groups of the polyamide A), 0.2: 1 to 2: 1, in particular 0.3: 1 to 1.5: 1 and more preferably 0.5: 1 to 0.8: 1. If 1 mol of the compound B) liberates more than 1 mol of isocyanic acid, correspondingly less compound B) is to be used, ie the stated molar ratio strictly refers to the isocyanic acid liberated from the compound B).
- the compounds B) are commercially available or their preparation is known to the person skilled in the art.
- the compound B) can be used as such, or dissolved or suspended in a suitable solvent or suspending agent.
- suitable solvents are, for example, alcohols having 1 to 10 carbon atoms, in particular methanol, ethanol or the propanols.
- the molecular weight of the polyamide increases particularly strongly when copper compounds C) are also used. They are therefore used in particular when polyamides are to be produced with a particularly high molecular weight.
- the process is preferably characterized in that one uses in addition to the components A) and B) a copper compound C).
- Suitable copper compounds C) are in particular those of monovalent or divalent copper. Suitable examples are the salts of mono- or divalent copper with inorganic or organic acids or monohydric or polyhydric phenols, the oxides of monovalent or divalent copper, or the complex compounds of copper salts with ammonia, amines, amides, Lactams, cyanides or phosphines. Preferably, the Cu (I) and Cu (II) salts of the hydrohalic acids, the hydrocyanic acid or the copper salts of the aliphatic carboxylic acids are used.
- a copper compound C) is also used, its amount is 0.001 to 1, preferably 0.005 to 0.5, in particular 0.005 to 0.3 and particularly preferably 0.01 to 0.2 wt .-%, based on the sum of components A. ), B) and C).
- the copper compounds C) are commercially available or their preparation is known in the art.
- the copper compound C) can be used as such, or preferably in the form of concentrates.
- Concentrate is understood to mean a polymer which contains the copper compound in a large amount, for example from 1 to 30% by weight, based on the concentrate.
- the polymer preferably has the same or a similar chemical nature as the polyamide A), that is to say it is preferably likewise a polyamide.
- the use of concentrates is a common method, especially for dosing small amounts of a feedstock to a polymer.
- Suitable further components are, in particular, additives or processing aids commonly used in polymers or in their preparation.
- the required amounts vary depending on the additive or auxiliary and are in a known manner u.a. after the intended use of the high molecular weight polyamide. See, e.g. Gumbleter / Müller, Plastics Additives Handbook, 4th ed., Hanser-Verlag Kunststoff, 1993, reprint Nov. 1996
- the additives or auxiliaries can either be used in the process according to the invention, ie the preparation of the high molecular weight polyamide from the components A), B) and optionally C), or the high molecular weight polyamide can be prepared first and later in one further step (so-called compounding) to add the additives or processing aids to the high molecular weight polyamide.
- Suitable additives or processing aids are e.g. Lubricants or mold release agents, rubbers, antioxidants, light stabilizers, antistatics, flame retardants, fibrous and pulverulent fillers or reinforcing agents, nucleating agents, organic or inorganic colorants (dyes or pigments) and other additives, or mixtures thereof ,
- Suitable lubricants and mold release agents are, for example, stearic acids, stearyl alcohol, stearic esters or amides, silicone oils, metal stearates, montan waxes and those based on polyethylene and polypropylene.
- Suitable antioxidants heat stabilizers
- Suitable antioxidants are, for example, sterically hindered phenols, hydroquinones, arylamines, phosphites, various substituted representatives of this group, and mixtures thereof. They are available commercially as Topanol®, Irgafos®, Irganox® or Naugard®.
- the copper compounds C) can also act as antioxidants, in particular together with metal halides, preferably alkali metal halides, eg NaI, KI, NaBr or KBr.
- Suitable anti-light stabilizers are e.g. various substituted resorcinols, salicylates, benzotriazoles, benzophenones, Hindered Amine Light Stabilizers (HALS), as described e.g. commercially available as Tinuvin®.
- HALS Hindered Amine Light Stabilizers
- Suitable antistatic agents are, for example, amine derivatives such as N, N-bis (hydroxyalkyl) alkylamines or -alkyleneamines, polyethylene glycol esters or glycerol mono- and distearates, and mixtures thereof.
- Suitable flame retardants are e.g. the halogen-containing or phosphorus-containing compounds known to those skilled in the art, magnesium hydroxide, red phosphorus, as well as other common compounds or mixtures thereof.
- fibrous or pulverulent fillers and reinforcing materials are carbon fibers or glass fibers in the form of glass fabrics, glass mats or glass silk rovings, chopped glass, glass beads and wollastonite, particularly preferably glass fibers.
- glass fibers When glass fibers are used, they can be equipped with a size and a bonding agent for better compatibility with the blend components.
- the incorporation of the glass fibers can take place both in the form of short glass fibers and in the form of endless strands (rovings).
- Suitable particulate fillers are e.g. Carbon black, amorphous silicic acid, magnesium carbonate, calcium carbonate, chalk, powdered quartz, mica, mica, bentonite, talcum, feldspar or in particular calcium silicates such as wollastonite and kaolin.
- Suitable nucleating agents are e.g. Talc, carbon black, polyamides having a higher melting point than component A), fluoropolymers such as polytetrafluoroethylene (PTFE), titanium dioxide, calcium phenylphosphinate, aluminum oxide, magnesium oxide or other metal oxides or carbonates.
- PTFE polytetrafluoroethylene
- Suitable colorants are all organic or inorganic dyes or pigments which are suitable for coloring. Polymers are suitable, see eg Plastics Additi ves Handbook, pages 637-708. Implementation of the components
- the conversion temperature within this range is to be selected such that the compound B) liberates isocyanic acid, ie the required minimum temperature depends inter alia on the compound B).
- the reaction takes place in a melt of the polyamide A), and the lower temperature limit results in this case also from the softening temperature of the polyamide.
- the upper temperature limit is usually determined by the thermal resistance of the polyamide, and the temperature is usually selected so that thermal damage to the polyamide is avoided.
- the reaction temperature is preferably 200 to 300, more preferably 240 to 28O 0 C.
- the pressure prevailing during the reaction is usually not critical.
- the process according to the invention can be carried out batchwise or continuously.
- conventional mixing devices such as mixers, kneaders or - preferably - extruder are suitable. They are usually tempered to adjust the temperature required for the reaction, wherein usually a part of the Cyprus ⁇ energy is already generated by the shear associated with the mixing process, and the remaining part is supplied by heating the mixing device.
- mixers with moving tools e.g. Worm belt mixers, double spiral mixers, paddle mixers, plowshare mixers, paddle mixers, slow or fast moving slurry mixers, cone screw mixers, silo-vertical screw mixers, agitator mixers (also agitator planetary mixers) or rolling mills, which are operated discontinuously or continuously depending on design.
- moving tools e.g. Worm belt mixers, double spiral mixers, paddle mixers, plowshare mixers, paddle mixers, slow or fast moving slurry mixers, cone screw mixers, silo-vertical screw mixers, agitator mixers (also agitator planetary mixers) or rolling mills, which are operated discontinuously or continuously depending on design.
- Suitable kneaders are e.g. Punch kneader and trough kneader (also double-bladed).
- Suitable extruders are all conventional screw machines, in particular single-screw and twin-screw extruders (eg ZSK from Coperion or Werner & Pfleiderer), co-kneaders, Kombiplast machines, MPC kneading mixers, FCM mixers, KEX kneading screw extruders and shear roller extruders , Preferably, the reaction takes place in an extruder.
- single-screw and twin-screw extruders eg ZSK from Coperion or Werner & Pfleiderer
- co-kneaders eg ZSK from Coperion or Werner & Pfleiderer
- Kombiplast machines eg., MPC kneading mixers, FCM mixers, KEX kneading screw extruders and shear roller extruders
- the reaction takes place in an extruder.
- Mischvorrichtun ⁇ gen Details of the mentioned and other, also suitable Mischvorrichtun ⁇ gen called, for example, the mentioned plastic paperback book Saechtling on page 202 - 250.
- the mixing device and its configuration, in particular the type and speed of the mixing tool and the quantities supplied and the throughput of Mischvorrich ⁇ tion are chosen in a known manner such that the compound B) release isocyanic acid and these, and optionally also the copper compound C), can react with the polyamide A).
- the speed, length, diameter and configuration of the extruder screw (s) eg number and depth of flights, pitch, sequence of conveying, kneading and mixing elements along the screw
- the extruder screw eg number and depth of flights, pitch, sequence of conveying, kneading and mixing elements along the screw
- the reaction time (duration of the reaction) is generally 10 seconds to 60 minutes, preferably 20 seconds to 30 minutes and in particular 25 seconds to 10 minutes.
- the average residence time with reaction time is e.g. in the extruder, meant.
- the components A), B) and optionally C) can first be premixed "cold” and this mixture can be fed to the mixing device in which the reaction takes place at the reaction temperature. and mix the thus treated polyamide, optionally together with the copper compound C), in the extruder at the reaction temperature and extrude the mixture, this embodiment being preferred.
- the application of the compound B) to the polyamide A for example, by spraying the polyamide granules with a solution or suspension of the compound B), or by tumbling such a solution or Sus ⁇ pension on the polyamide A), take place .
- a solution of B e.g. an alcoholic solution, for example in ethanol.
- the polyamide granules treated with compound B), if appropriate together with the copper compound C are fed to the extruder where the reaction takes place.
- the product obtained is a high molecular weight polyamide.
- the high molecular weight polyamide withdrawn from the mixing device is generally melt-liquefied. sig. It is solidified in the usual way, for example, passed through a water bath, and granulated or otherwise broken up.
- the inventive method is characterized in that the high molecular weight polyamide obtained has a viscosity number (VZ) of 120 to 400 ml / g, determined according to ISO 307 EN on a 0.5 wt .-% solution of Polya ⁇ mids in 96 wt .-% sulfuric acid at 25 ° C.
- VZ viscosity number
- the Vis ⁇ kosticiansiere is 150 to 350, in particular 180 to 320 ml / g.
- the method is characterized in that the high molecular weight polyamide volatile bases (FB) has.
- the concentration of the volatile bases depends, for example, on the carbonyl end group concentration of the polyamide A) and the amount of compound B) used, and is preferably at least 1 mmol of FB per kg of high molecular weight polyamide.
- the determination of the volatile bases can be carried out, for example, by acid hydrolysis of the high molecular weight polyamide, liberation of the bases by addition of a strong base, overdistillation of the bases liberated into an acidic template and back-titration of the excess template acid in the presence of an indicator ,
- the high molecular weight polyamide is first hydrolyzed by boiling with hydrochloric acid with attached riser. After cooling the mixture, the riser is replaced by dropping funnel and distillation, NaOH excessively added dropwise and distilled over the liberated bases in a template, where they are absorbed by excess hydrochloric acid. Subsequently, the über ⁇ schüssige hydrochloric acid of the template is back titrated with NaOH and Bromkresolrot as an indicator and calculated from the NaOH consumption, the concentration of free base.
- the invention also relates to the high molecular weight polyamide obtainable by this process.
- the high molecular weight polyamide can be used as such or blended with other polymers, ie in a polymer blend.
- Such other polymers are, in particular, customary polyamides (see description of component A)), and chewing polymers which impact-modify the polyamide.
- Suitable rubber polymers are in particular diene rubbers such as polybutadiene or styrene-butadiene copolymers, acrylate rubbers such as poly-n-butyl acrylate, ethylene rubbers such as EPM and EPDM (ethylene-propylene (diene) monomer), and silicone rubbers.
- the rubber can also be constructed as core-shell rubber (graft rubber), random copolymer rubber or block copolymer rubber.
- Moldings of all kinds, foils, fibers (including filaments and monofilaments) and foams can be produced from the high molecular weight polyamide.
- the invention therefore also relates to the use of the high molecular weight polyamides for the production of moldings, films, fibers and foams, and the moldings, films, fibers and foams from the high molecular weight polyamides.
- the production process according to the invention for high molecular weight polyamides is simpler than the processes of the prior art and does not require any expensive solid-phase condensation.
- the desired increase in molecular weight is achieved in a particularly problem-free manner by simply adding urea or another isocyanic acid-releasing compound to a conventional, non-high molecular weight polyamide.
- Another subject of the invention is a process for increasing the molecular weight of polyamides ("raising process"), characterized in that a polyamide A), wherein the concentration of the amino end groups is greater than or equal to the concentration of the carboxyl end groups, at a temperature of 150 to 350 ° C with a compound B), which releases isocyanic acid at this reaction temperature.
- the enhancement method is characterized by at least one feature as defined in the characterizing part of claims 1 to 10.
- A2 polyamide 6 prepared with bis (hexamethylene) triamine as a chain regulator; AEK> CEK
- the polyamide present as granules was dried at 80 ° C. in vacuo ( ⁇ 100 mbar) to a water content ⁇ 0.1% by weight.
- the urea was applied to the dried polyamide granules by tumbling the ethanolic urea solution at 25 ° C. onto the granules with partial evaporation of the ethanol.
- the amount of urea solution was measured so that the granules obtained had the urea content shown in Table 1.
- the granules treated in this way were dried for about 2 hours at 40 ° C. in vacuo ( ⁇ 100 mbar) in order to remove residues of adhering ethanol.
- Viscosity number VZ determined according to ISO 307 EN on a 0.5% strength by weight solution of the polymer in 96% strength by weight sulfuric acid at 25 ° C.
- Amino end group concentration AEK 25 ml of a mixture of 75% by weight of phenol and 25% by weight of methanol were added to 1 g of the polymer and the mixture was boiled for 20 minutes while stirring and refluxing. Thereafter, the mixture was allowed to cool 20 0 C and gave ab ⁇ 3 drops of an indicator solution (65 mg and 35 mg of benzyl Me ⁇ thylenblau dissolved in methanol and methanol to 100 ml with padding). It was then treated with 0.02 N perchloric acid solution (1.72 ml of 70% perchloric acid with 100 ml of methanol, make up to 1000 ml with ethylenglycol) until the color change. titrated from green to red and calculates the AEK from the perchloric acid consumption.
- Carboxyl end group concentration CEK 25 ml of benzyl alcohol were added to 1 g of the polymer and the mixture was boiled for 25 min while stirring with attached riser and nitrogen gas introduction. 6 drops of an indicator solution were then added to the still hot mixture (100 mg of cresol red in 100 ml of 1-propanol) and titrated immediately with a 0.02 N potassium hydroxide solution (5.61 g KOH in methanol and 100 ml of methanol make up to 20 ml with 430 ml of 1-propanol and 550 ml of 1-hexanol to 1000 ml of this solution) until the color changes from yellow to violet.
- the CEK was calculated from the consumption of KOH.
- AEK, CEK and FB are given in mmol per kg of polymer.
- Tables 1 and 2 summarize the compositions and the results of the measurements.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007524246A JP4605811B2 (ja) | 2004-08-04 | 2005-07-30 | 高分子ポリアミドの製造方法 |
US11/659,285 US20080312353A1 (en) | 2004-08-04 | 2005-07-30 | Process for Preparation of High-Molecular-Weight Polyamides |
EP05777287A EP1776409B1 (de) | 2004-08-04 | 2005-07-30 | Verfahren zur herstellung hochmolekularer polyamide |
DE502005004039T DE502005004039D1 (de) | 2004-08-04 | 2005-07-30 | Verfahren zur herstellung hochmolekularer polyamide |
MX2007000915A MX2007000915A (es) | 2004-08-04 | 2005-07-30 | Metodo para la produccion de poliamidas de peso molecular alto. |
KR1020077005097A KR101188589B1 (ko) | 2004-08-04 | 2005-07-30 | 고분자량 폴리아미드의 제조 방법 |
US12/711,313 US20100152313A1 (en) | 2004-08-04 | 2010-02-24 | Process for preparation of high-molecular-weight polyamides |
Applications Claiming Priority (2)
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DE102004038014.7 | 2004-08-04 | ||
DE102004038014A DE102004038014A1 (de) | 2004-08-04 | 2004-08-04 | Verfahren zur Herstellung hochmolekularer Polyamide |
Related Child Applications (1)
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US12/711,313 Continuation US20100152313A1 (en) | 2004-08-04 | 2010-02-24 | Process for preparation of high-molecular-weight polyamides |
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PCT/EP2005/008275 WO2006015743A1 (de) | 2004-08-04 | 2005-07-30 | Verfahren zur herstellung hochmolekularer polyamide |
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US (2) | US20080312353A1 (de) |
EP (1) | EP1776409B1 (de) |
JP (1) | JP4605811B2 (de) |
KR (1) | KR101188589B1 (de) |
CN (1) | CN100537637C (de) |
AT (1) | ATE394444T1 (de) |
DE (2) | DE102004038014A1 (de) |
ES (1) | ES2306201T3 (de) |
MX (1) | MX2007000915A (de) |
MY (1) | MY140308A (de) |
WO (1) | WO2006015743A1 (de) |
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JP2015199873A (ja) * | 2014-04-09 | 2015-11-12 | 旭化成ケミカルズ株式会社 | 強化高分子量ポリアミド樹脂組成物 |
TWI647253B (zh) * | 2016-12-29 | 2019-01-11 | 大東樹脂化學股份有限公司 | 利用芳香族氨甲酸酯透過異氰酸鹽作為前驅物之經催化熱反應路徑以製備醯胺或聚醯胺的方法及由芳香胺製備芳香族氨甲酸酯前驅物的方法 |
DE102017216814A1 (de) * | 2017-09-22 | 2019-03-28 | Adidas Ag | Verfahren zum Herstellen eines Formteils und Formteil |
KR102262531B1 (ko) * | 2017-11-28 | 2021-06-08 | 한화솔루션 주식회사 | 아마이드계-분자량조절제를 포함하는 폴리아마이드 제조방법 및 이에 의해 제조된 폴리아마이드 |
CA3118466C (en) * | 2018-11-09 | 2023-05-16 | Advansix Resins & Chemicals Llc | Stain resistant polyamide polymers obtained via high end group termination |
CN113999389B (zh) * | 2021-11-19 | 2022-12-06 | 四川大学 | 一种长链尼龙与缩二脲的共聚物的薄膜及其制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1595603A1 (de) * | 1966-03-12 | 1970-05-14 | Bayer Ag | Stabilisierte Polyamide |
US5280060A (en) * | 1990-08-02 | 1994-01-18 | Sumitomo Chemical Company, Limited | Thermoplastic resin composition containing a fluidity modifier |
Family Cites Families (6)
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JPS61171732A (ja) * | 1985-01-23 | 1986-08-02 | Unitika Ltd | 高重合度ポリアミドの製造法 |
JPS6222829A (ja) * | 1985-07-23 | 1987-01-31 | Teijin Ltd | 高重合度ポリアミドの製造法 |
JP2956160B2 (ja) * | 1990-08-02 | 1999-10-04 | 住友化学工業株式会社 | 熱可塑性樹脂組成物 |
JPH04122773A (ja) * | 1990-09-12 | 1992-04-23 | Unitika Ltd | ナイロン46組成物 |
DE10047657B4 (de) * | 2000-09-26 | 2005-02-10 | Basf Ag | Verfahren zur Herstellung von Polycaprolactam, ein Polycaprolactam und dessen Verwendung |
US6541599B1 (en) * | 2001-07-31 | 2003-04-01 | Eastman Kodak Company | Process for manufacture of soluble highly branched polyamides, and at least partially aliphatic highly branched polyamides obtained therefrom |
-
2004
- 2004-08-04 DE DE102004038014A patent/DE102004038014A1/de not_active Withdrawn
-
2005
- 2005-07-30 DE DE502005004039T patent/DE502005004039D1/de active Active
- 2005-07-30 WO PCT/EP2005/008275 patent/WO2006015743A1/de active IP Right Grant
- 2005-07-30 MX MX2007000915A patent/MX2007000915A/es active IP Right Grant
- 2005-07-30 JP JP2007524246A patent/JP4605811B2/ja not_active Expired - Fee Related
- 2005-07-30 KR KR1020077005097A patent/KR101188589B1/ko active IP Right Grant
- 2005-07-30 US US11/659,285 patent/US20080312353A1/en not_active Abandoned
- 2005-07-30 EP EP05777287A patent/EP1776409B1/de not_active Not-in-force
- 2005-07-30 AT AT05777287T patent/ATE394444T1/de not_active IP Right Cessation
- 2005-07-30 CN CNB2005800265980A patent/CN100537637C/zh active Active
- 2005-07-30 ES ES05777287T patent/ES2306201T3/es active Active
- 2005-08-01 MY MYPI20053549A patent/MY140308A/en unknown
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2010
- 2010-02-24 US US12/711,313 patent/US20100152313A1/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1595603A1 (de) * | 1966-03-12 | 1970-05-14 | Bayer Ag | Stabilisierte Polyamide |
US5280060A (en) * | 1990-08-02 | 1994-01-18 | Sumitomo Chemical Company, Limited | Thermoplastic resin composition containing a fluidity modifier |
Also Published As
Publication number | Publication date |
---|---|
EP1776409B1 (de) | 2008-05-07 |
ATE394444T1 (de) | 2008-05-15 |
DE102004038014A1 (de) | 2006-03-16 |
KR101188589B1 (ko) | 2012-10-08 |
CN1993402A (zh) | 2007-07-04 |
DE502005004039D1 (de) | 2008-06-19 |
MY140308A (en) | 2009-12-31 |
JP4605811B2 (ja) | 2011-01-05 |
EP1776409A1 (de) | 2007-04-25 |
KR20070050943A (ko) | 2007-05-16 |
MX2007000915A (es) | 2007-04-16 |
ES2306201T3 (es) | 2008-11-01 |
US20100152313A1 (en) | 2010-06-17 |
US20080312353A1 (en) | 2008-12-18 |
JP2008508409A (ja) | 2008-03-21 |
CN100537637C (zh) | 2009-09-09 |
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